Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/10—Electroplating with more than one layer of the same or of different metals
  • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/48—After-treatment of electroplated surfaces
  • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/615—Microstructure of the layers, e.g. mixed structure
  • C25D5/617—Crystalline layers
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/117—Inorganic material
  • H01M50/119—Metals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
  • H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
  • H01M50/133—Thickness
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/24—Alkaline accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0002—Aqueous electrolytes
  • H01M2300/0014—Alkaline electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
  • H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12771—Transition metal-base component
  • Y10T428/12861—Group VIII or IB metal-base component
  • Y10T428/12937—Co- or Ni-base component next to Fe-base component

Definitions

• the present invention relates to a surface treated steel sheet used for an electric battery container, particularly to a surface treated steel sheet used for a container of a first battery such as an alkaline battery or a manganese battery, a battery container with the surface treated steel sheet and a battery.
• a first battery such as an alkaline battery or a manganese battery
• an adhesive characteristic between an inner surface of a container and positive electrode active material is strengthened.
• various methods for reducing internal resistance of the container after finishing a step of forming a hard plating layer made from nickel-phosphorous alloy or nickel-tin alloy and so on.
• the nickel-tin alloy is superior in view of reducing the internal resistance, there is a drawback. That is, a discharging characteristic is deteriorated while the alloy layer is contacted with alkaline liquid for a long time.
• a present invention is developed by utilizing a feature that Bismuth metal has an excellent anti-alkaline characteristic so that compounds of a plating layer is not solved even if the bismuth metal is contacted with alkaline solution for a long time and another feature that the metal is apt to be diffused so that an alloy layer can be formed easily. According to these features, it can be accomplished to provide a battery of which the discharging characteristic is not deteriorated for a long time by employing metal including bismuth metal as an inner surface of a battery container.
• a method according to the present invention is characterized in that a surface treated steel sheet for a battery container in which a nickel-bismuth alloy layer is formed on at least one surface of the steel sheet and the alloy layer is formed by an electrolyte plating method and an inner surface of the battery container is made of metal combined by a steel sheet for a battery container and a steel sheet in which the nickel-bismuth alloy layer is diffused. If a steel sheet made of only bismuth metal is used, the layer is apt to be peeled. Once the layer begins being peeled, the inner nickel layer contacts with alkaline solution directly. Such a phenomenon is unlikely.
• the carbon powder it is required high purity and chemical stability, good conductivity, processability of mixed material and a characteristic for holding solution.
• acetylene black, denatured products of carious carbon black, graphitized carbon black and synthetic graphite powder have been utilized as carbon black satisfied with the above requirements.
• synthetic graphite is mainly used.
• a ratio of electrolyte dioxide manganese with respect to graphite is 5:1 to 10:1.
• potassium hydroxide solution is added to them so as to mix the materials in accordance with a proper method.
• mixture of organic solvents such as graphite, thermosetting resin, methyl ethyl ketone and so on is coated on an inner surface of the battery container by a spray method and so on and then dried.
• the mixture is pressurized in a mold so as to form a donut-shaped positive electrode active material pellet.
• the pellet is attached to an inside of the battery container and pressurized.
• a cathode board on which a cathode collecting bar is spot-welded is attached to a battery container by neck-in processing at a predetermined location of a lower portion of an opening end of the battery container.
• a purpose of a separator used for a battery is to prevent particles of negative active material and its products and particles of cathodic active material from moving mutually. Thereby, inner short circuit and self-discharging of a battery container be prevented by avoiding for producing the cathode products in the separator.
• Fiber material or non-woven fiber having anti-alkaline characteristic is used as the separator.
• synthetic resin such as vinylon, polyolefin, polyamide and so on, linter pulp, mercerization wooden pulp or reproduced cellulose of which ⁇ -cellulose content is equal or more than 98 % are used.
• One of these kinds of fiber separator is inserted along an inner surface of the positive electrode active material pellet pressurized at the battery container.
• Anode gel made of potassium hydroxide that zinc grains and zinc oxide are saturated is inserted into a battery container.
• the zinc grains it is preferably atomizing powder of which a diameter is about 200 ⁇ m.
• the gel starch, cellulose derivative, polyacrylate and so on may be used.
• an insulate gasket is attached to the cathode member, inserted into the battery container, and caulked so as to manufacture an alkaline manganese battery.
• a steel sheet is a cold rolled steel sheet with a thickness of 0.25 mm and has been annealed and then skin-passed.
• Components of the steel sheet which is a plating board are carbon of 0.03 wt%, manganese of 0.21 wt%, silicone of 0.01 wt%, phosphorus of 0.01 wt%, sulfur of 0.06 wt%, aluminum of 0.035 wt% and nitrogen of 0.0024 wt%.
• the steel sheet is immersed into solution in which sodium hydroxide (NaOH) of 30 g/L is solved at 70 °C and alkaline electrolytic degreasing is treated at current density of 5 A/dm 2 for 10 seconds.
• NaOH sodium hydroxide
• the steel sheet After alkaline degreasing, the steel sheet is immersed in sulfuric solution of 50 g/L for 15 seconds so as to neutralize by acid cleaning. Then, while a nickel pellet attached with a polypropylene bag is affected as an anode, the steel sheet is plated by air stirring so as to form a matte nickel plating layer with a thickness of 2.2 ⁇ m in accordance with the following condition.
• Bath components Nickel sulfate 300g/L Nickel chloride 45g/L Boric acid 45g/L Pitless Agent 0.5g/L Bath temperature 58 ⁇ 2 °C pH 4.0 ⁇ 0.2 Current density 25A/dm 2
• a bismuth plating layer having a thickness of 0.22 ⁇ m is formed in the following bismuth chloride bath.
• Bath components Meta-sulfonic acid 150g/L Bismuth( 2+ ) 20g/L Diffusing agent 10g/L Gloss agent 10ml/L Bath temperature 22 ⁇ 2 °C pH 0.5 Current density 3A/dm 2
• a thermal treatment is operated by a box type annealing furnace at 300 °C for 300 minutes so as to denature the nickel-bismuth plating layer to a nickel-bismuth alloy layer.
• atmosphere gas is hydrogen of 6 % and the other is nitrogen gas and a dew-point temperature is -45 °C.
• a thickness of a nickel layer is 0.24 ⁇ m.
• an iron-nickel diffused layer and triple diffused layers of nickel, bismuth and iron have not been formed, it can be recognized that the nickel-bismuth diffused layer with a thickness of 1.90 ⁇ m is formed.
• a thickness of a nickel-bismuth plating layer, a thermal treatment condition and a judgement condition of a cross sectional view of a steel sheet after finishing a step of the thermal treatment are shown in Table 1.
• a battery container is made of a plated steel sheet in accordance with the DI method. After cupping a blank diameter of 41 mm of the thermal treated steel sheet with a thickness of 0.25 mm to a diameter of 20.5 mm, re-drawing and two step drawing are operated in a DI machine so as to form a container of which an outer diameter is 13.8 mm, a thickness is 0.20 mm and a height is 56 mm. In the final, trimming is operated with respect to an upper portion of the battery so as to produce a LR-6 type battery container with a height of 49.3 mm. Positive electrode active material is filled into the battery container. A performance of a manufactured battery is measured.
• Manganese dioxide and graphite in which a ratio of manganese dioxide with respect to graphite is 10:1 are collected and mixed with potassium hydroxide of 8 ml so as to produce positive electrode active material.
• mixture of graphite of 80 wt% and thermosetting epoxy resin of 20 wt% are diluted with methyl ethyl ketone.
• the dilution liquid is sprayed on an inner surface of a battery container and then dried at 150 °C for 15 min.
• the positive electrode active material is pressurized in a mold so as to form a donut-shaped mixture material pellet.
• the pellet is inserted into an inside of a battery container and pressurized.
• a cathode board on which a cathode collecting bar is spot-welded is attached to a battery container by neck-in processing at a predetermined location of a lower portion of an opening end of the battery container.
• a separator made of vinylon unwoven fiber is inserted along an inner peripheral surface attached to the battery container.
• anode gel made from potassium hydroxide saturated by zinc grains and zinc oxide is inserted into the battery container.
• an insulate gasket is attached to the cathode member and inserted into the battery container.
• an alkaline manganese battery is furnished by caulking. The furnished alkaline manganese battery is maintained at 60 °C for 20 days.
• An inner resistance, a short circuit current and 2 ⁇ continuous discharging time (min) are measured and the result thereof is shown in Table 3.
• a steel sheet having the same quality and the same thickness of the example 1 is used.
• mutt nickel plating is processed.
• bismuth plating is processed.
• a thickness of a plating layer is controlled by adjusting a plating time.
• the steel sheet is operated in a box type annealing furnace in the same atmosphere of the example 1.
• a thermal treatment is processed for 480 min wherein a heating temperature is varied in a range of 450 °C to 600 °C.
• characteristics are measured and shown in Table 1.
• an alkaline manganese battery is manufactured by using the thermal treated steel sheet. Battery characteristics thereof are shown in Table 3.
• a steel sheet having the same quality and the same thickness of the example 1 is used. Characteristics of the steel sheet which is only nickel plated are shown in Table 2. Battery characteristics made of the steel sheet are shown in Table 3. Comparative examples 1 and 2 show samples without thermal treatment and comparative example 3 and 4 show samples with thermal treatment. The comparative example 3 is thermally treated at 500 °C for 300 min. The comparative example 4 is thermally treated at 600 °C for 480 min. Characteristics and a cross sectional condition of a steel sheets after finishing a step of plating and steel sheets after finishing a step of thermal treatment are shown in Table 2. As similar as the example 1, an alkaline manganese battery is made of the surface treated steel sheet. A respective inner resistance and so on of the alkaline manganese batteries are shown in Table 3.
• Characteristics of the respective steel sheet and the respective battery of the embodiments and the comparisons are measured by the following method.
• an alkaline manganese battery in which a steel sheet with a nickel-bismuth diffused layer is used as a positive board has an inner resistance smaller than that of a conventional alkaline manganese battery in which a mutt nickel plated steel sheet, that is, a typically polar board of a battery sold in the market is used.
• the alkaline manganese battery according to the present invention is excellent in view of short circuit current. Regarding the continuous discharging time, it can be found a clear difference distinguishable from the conventional alkaline manganese battery.

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• Chemical & Material Sciences (AREA)
• Electrochemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Sealing Battery Cases Or Jackets (AREA)
• Electroplating Methods And Accessories (AREA)
• Primary Cells (AREA)

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• 1999
  • 1999-05-27 EP EP99922517A patent/EP1111697A1/de not_active Withdrawn
  • 1999-05-27 KR KR1020017001119A patent/KR100589884B1/ko not_active Expired - Fee Related
  • 1999-05-27 WO PCT/JP1999/002795 patent/WO2000074155A1/ja not_active Ceased
  • 1999-05-27 AU AU39542/99A patent/AU3954299A/en not_active Abandoned
  • 1999-05-27 US US09/744,649 patent/US6551721B1/en not_active Expired - Fee Related
  • 1999-05-27 CN CNB998099279A patent/CN1181570C/zh not_active Expired - Fee Related

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